WO2019176919A1

WO2019176919A1 - Method for producing carbodiimide compound

Info

Publication number: WO2019176919A1
Application number: PCT/JP2019/009934
Authority: WO
Inventors: 展幸松本; 健一柳沢
Original assignee: 日清紡ケミカル株式会社
Priority date: 2018-03-12
Filing date: 2019-03-12
Publication date: 2019-09-19
Also published as: JP2023060066A; US20230106672A1; TW201940463A; CN111836797A; EP3766863A4; US20210009512A1; EP3766863A1; KR20200130299A; JPWO2019176919A1; JP7239556B2

Abstract

A method for producing a carbodiimide compound, the method comprising a carbodiimide generation step in which an aliphatic tertiary isocyanate compound (A) is reacted in the presence of an organic alkali metal compound (B) having Lewis basicity.

Description

Method for producing carbodiimide compound

The present invention relates to a method for producing a carbodiimide compound, and more particularly to a method for producing a carbodiimide compound from an isocyanate. The present invention also relates to a method for producing polyurethane, the use of a carbodiimide compound, a carbodiimide composition, a stabilizer, and an ester resin composition.

The carbodiimide compound is useful for various applications such as stabilizers for various resins such as thermoplastic resins and hydrolysis inhibitors.
When producing a carbodiimide compound from isocyanate, it is known to use an organophosphorus catalyst as a carbodiimidization catalyst.
For example, Patent Document 1 describes that polyisocyanate is reacted in the presence of a phosphorus-containing catalyst to form polyisocyanate carbodiimide.
Patent Document 2 discloses 1-phenyl-2-phospholene 1-oxide, 3-methyl-1-phenyl-2-phospholene 1-oxide, 1-phenyl-2-phospholene 1-sulfide as a carbodiimide-forming catalyst. 1-ethyl-2-phospholene 1-oxide, 1-ethyl-3-methyl-2-phospholene 1-oxide, and the corresponding isomeric 3-phospholenes are mentioned.

In addition, it is known to use an organometallic compound as an isocyanurate-forming catalyst when isocyanate is modified with isocyanurate.
For example, Patent Document 3 describes the use of an alkali metal salt of a carboxylic acid and a tertiary amine as a catalyst for promoting a trimerization reaction (isocyanuration reaction) of an isocyanate. In the publication, alkali metal salts of carboxylic acids such as sodium acetate, potassium acetate, potassium 2-ethylhexoate, potassium adipate, sodium benzoate and the like are mentioned as the alkali metal salts of the carboxylic acid. In the publication, N-alkylethyleneimine, N- (2-dimethylaminoethyl) -N′-methylpiperazine and tris-3-dimethylaminopropylhexahydro-s-triazine are used as the tertiary amine. Are listed.

JP 51-37996 A JP-A-51-61599 JP 50-159593 A

The organophosphorus compounds used as carbodiimidization catalysts in Patent Documents 1 and 2 are very expensive compounds.
In addition, when a carbodiimide compound is produced using the organophosphorus compound, there is a problem that the organophosphorus compound remaining in the obtained carbodiimide compound interferes with the counterpart material and is difficult to use. In order to solve this problem, a method in which the catalyst is distilled off under reduced pressure during or after the synthesis of the carbodiimide compound is known, but there is a problem that the process becomes complicated.

The present invention has been made to solve the above-described problems, and produces a carbodiimide compound in a high yield from an isocyanate compound even when an organophosphorus compound is not substantially used as a carbodiimidization catalyst. It is an object to provide a method, a method for producing polyurethane, use of a carbodiimide compound, a carbodiimide composition, a stabilizer, and an ester resin composition.

As a result of intensive studies, the present inventors have found that organic alkali metal compounds among organic metal compounds that have been conventionally used as isocyanurate catalysts are useful as carbodiimidization catalysts for specific isocyanates. Accordingly, it has been found that when the catalyst is removed, it can be removed by a simple method.

That is, the present invention provides the following [1] to [10].

[1] A method for producing a carbodiimide compound, comprising a carbodiimide production step in which an aliphatic tertiary isocyanate compound (A) is reacted in the presence of an organic alkali metal compound (B) having Lewis basicity.
[2] The method for producing a carbodiimide compound according to [1] above, wherein the organic alkali metal compound (B) having Lewis basicity is at least one of a metal alkoxide, a metal amide, and a metal carboxylate.
[3] The above [1] or [3], wherein the aliphatic tertiary isocyanate compound (A) has at least one aromatic ring bonded to a tertiary carbon atom to which an isocyanate group is bonded. [2] A method for producing a carbodiimide compound according to [2].
[4] The above [1] to [3], wherein the aliphatic tertiary isocyanate compound (A) is at least one of tetramethylxylylene diisocyanate and 3-isopropenyl-α, α-dimethylbenzyl isocyanate. The manufacturing method of the carbodiimide compound in any one.
[5] In the carbodiimide production step, the aliphatic tertiary isocyanate compound (A) is reacted in the presence of the Lewis basic organic alkali metal compound (B) and the phase transfer catalyst (C). [1] The method for producing a carbodiimide compound according to any one of [4].
[6] The carbodiimide compound according to [5], wherein the phase transfer catalyst (C) is at least one of a crown ether, a quaternary ammonium salt, and a compound represented by the following general formula (1). Production method.

(In Formula (1), X and Y are each independently a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group. R ¹ is an alkylene group having 2 to 3 carbon atoms. m is an integer of 2 to 500.)
[7] A part of the isocyanate group in the aliphatic tertiary isocyanate compound (A) is added to at least one of the three time points before the carbodiimide production step, during the production step, and after the production step. A sealing step of sealing with a terminal blocking agent, wherein the terminal blocking agent is a compound (D-1) represented by the following general formula (2-1): ] The manufacturing method of the carbodiimide compound in any one of.

(In the formula (2-1), Z is a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group. R ² is an alkylene group having 2 to 3 carbon atoms. It is an integer of 500.)
[8] A part of the isocyanate group in the aliphatic tertiary isocyanate compound (A) is added to at least one of the three time points before the carbodiimide production step, during the production step, and after the production step. Any one of the above-mentioned [1] to [7], wherein the chain extender is reacted with a chain extender, and the chain extender is a compound (D-2) represented by the following general formula (2-2): A method for producing a carbodiimide compound according to claim 1.

(In the formula (2-2), R ³ is an alkylene group having 2 to 3 carbon atoms. P is an integer of 2 to 500.)
[9] The above [1] to [8], further comprising an adsorption removal step of adsorbing and removing the Lewis basic organic alkali metal compound (B) using an adsorbent (E) after the carbodiimide production step. ] The manufacturing method of the carbodiimide compound in any one of.
[10] The adsorbent (E) is a synthetic aluminum silicate adsorbent, synthetic magnesium silicate, acidic cation exchange resin, basic anion exchange resin, alumina, silica gel adsorbent, zeolite adsorbent, hydro The carbodiimide compound according to the above [9], which is at least one of talcite, magnesium oxide-aluminum oxide solid solution, aluminum hydroxide, magnesium oxide, and aluminum hydroxide-sodium hydrogen carbonate coprecipitate (dorsonite). Production method.
[11] The above [1] to [1] for producing a stabilizer having a purity of 90% by mass or more and containing no phospholene oxides or having a phospholene oxide content of 1 mass ppm or less. [10] A production method comprising the production method according to any one of [10].
[12] A process for producing a polyurethane, wherein a polyurethane, preferably a thermoplastic polyurethane, is obtained by reacting a polyol and a diisocyanate in the presence of a stabilizer.
The said stabilizer contains the aliphatic tertiary carbodiimide derived from an aliphatic tertiary isocyanate compound, and the manufacturing method of a polyurethane whose content of an alkali metal is less than 2000 mass ppm.
[13] The blending amount of the aliphatic tertiary carbodiimide derived from the aliphatic tertiary isocyanate compound with respect to 100 parts by mass of the total amount of the polyol and the diisocyanate is 0.1 to 2 parts by mass, preferably 0.5 The method for producing a polyurethane as described in [12] above, which is ˜1 part by mass.
[14] The aliphatic tertiary carbodiimide derived from the aliphatic tertiary isocyanate compound is preferably 20 to 50 ° C., particularly preferably 25 to 35 ° C., in liquid form, continuously or batchwise. The method for producing a polyurethane according to the above [12] or [13], characterized by being metered in.
[15] A process for producing a polyurethane, wherein a polyurethane, preferably a thermoplastic polyurethane, is obtained by reacting a polyol and a diisocyanate in the presence of a stabilizer.
A method for producing polyurethane, wherein the stabilizer is a carbodiimide compound produced by the method for producing a carbodiimide compound according to any one of [1] to [10].
[16] Use of the carbodiimide compound according to any one of [1] to [10] above to prevent hydrolysis.
[17] A carbodiimide compound having an aliphatic tertiary isocyanate compound (A) as a constitutional unit and an alkali metal and no phospholene oxides or a phospholene oxide content of 1 mass ppm A carbodiimide composition that is:
[18]
The carbodiimide composition according to the above [17], further containing a phase transfer catalyst (C).
[19] It contains a carbodiimide compound having an aliphatic tertiary isocyanate compound (A) as a structural unit and an alkali metal, and does not contain phospholene oxides, or the content of phospholene oxides is 1 mass. A stabilizer that is ppm or less.
[20] The stabilizer according to [19], further comprising a phase transfer catalyst (C).
[21] An ester resin composition comprising the carbodiimide composition according to the above [17] or “18” and an ester resin.
[22] The ester resin composition according to [21], wherein the content of the carbodiimide composition is 0.2 to 5.0 parts by mass with respect to 100 parts by mass of the ester resin.
[23] An ester resin composition comprising the stabilizer according to [19] or [20] above and an ester resin.

According to the present invention, even when an organophosphorus compound is not substantially used as a carbodiimidization catalyst, a carbodiimide compound can be produced in a high yield by reacting an aliphatic tertiary isocyanate compound.

Hereinafter, the present invention will be described in detail using embodiments.
1. Method for Producing Carbodiimide Compound The method for producing a carbodiimide compound according to the present embodiment is a method for producing a carbodiimide by reacting an aliphatic tertiary isocyanate compound (A) in the presence of an organic alkali metal compound (B) having Lewis basicity. It has a process.
As described above, the organic alkali metal compound usually acts as a catalyst for assisting the trimerization reaction (isocyanuration reaction) of isocyanate. However, when the aliphatic tertiary isocyanate compound (A) is reacted as an isocyanate, the organic alkali metal compound (B) having Lewis basicity acts as a carbodiimidization catalyst. Thereby, the production | generation of a dimer (uretdione), a trimer (isocyanurate), and another multimer is suppressed or prevented, and a carbodiimide compound can be obtained with a high yield.
In the method for producing a carbodiimide compound according to the present embodiment, it is preferable not to use an organic phosphorus compound substantially, and it is more preferable not to use it at all. When no organophosphorus compound is used, it is possible to omit the catalyst removal step after the carbodiimide is produced. However, even if an organophosphorus compound is not used, another catalyst removal step may be performed.

The manufacturing method of the carbodiimide compound which concerns on this Embodiment may have another process other than the said carbodiimide production | generation process. For example, for the purpose of controlling the molecular weight, the aliphatic tertiary isocyanate compound (A) is added to the aliphatic tertiary isocyanate compound (A) before the carbodiimide production step, during the production step, and at least one time point among the three time points after the production step. You may have a chain extension process which connects the isocyanate process and the sealing process which seals a terminal with the compound which has a functional group which reacts with isocyanate, and a part of derived isocyanate group.
For example, when performing a sealing process before a production | generation process, it is preferable to seal a part of isocyanate group of an aliphatic tertiary isocyanate compound (A). When the sealing step is carried out during the production step, a part of the terminal isocyanate group of the polycarbodiimide produced by the carbodiimidization reaction of the aliphatic tertiary isocyanate compound (A), and the aliphatic third before the reaction It is preferable to seal a part of the isocyanate group of the secondary isocyanate compound (A). When the sealing step is carried out after the polycarbodiimide is produced, it is preferable to seal all of the terminal isocyanate groups of the produced polycarbodiimide compound.
Moreover, when implementing a chain extension process before a production | generation process, it is preferable to provide a chain extension agent to a part of isocyanate group of an aliphatic tertiary isocyanate compound (A). When carrying out the chain extension step during the production step, a part of the terminal isocyanate group of the polycarbodiimide produced by the carbodiimidization reaction of the aliphatic tertiary isocyanate compound (A), and the aliphatic third before the reaction It is preferable to add a chain extender to a part of the isocyanate group of the secondary isocyanate compound (A). When the chain extension step is carried out after the polycarbodiimide is formed, it is preferable to add a chain extender to a part or all of the terminal isocyanate groups of the generated polycarbodiimide compound.
In addition, you may implement the said sealing process only before the said carbodiimide production | generation process, in the middle of a production | generation process, or after a production | generation process. Further, the chain extension step may be performed only before, during or after the carbodiimide generation step.
Moreover, you may have the adsorption removal process of adsorbing and removing the said organic alkali metal compound (B) which has the Lewis basicity using an adsorption agent (E) after the said carbodiimide production | generation process.
In addition, in the manufacturing method of the carbodiimide compound which concerns on this Embodiment, an organic phosphorus compound is not substantially used, Preferably it is not used at all. When no organophosphorus compound is used, it is possible to omit the catalyst removal step after the carbodiimide is produced. However, even if an organophosphorus compound is not used, another catalyst removal step may be performed.
Next, each step will be described.

[Carbodiimide production process]
The manufacturing method of the carbodiimide compound which concerns on this Embodiment has a carbodiimide production | generation process which makes an aliphatic tertiary isocyanate compound (A) react in presence of the organic alkali metal compound (B) which has Lewis basicity.

<Aliphatic tertiary isocyanate compound (A)>
In the present embodiment, the aliphatic tertiary isocyanate compound (A) means that the isocyanate group is directly connected to a carbon atom other than the aromatic ring, and the carbon atom directly connected to the isocyanate group is a tertiary atom. This refers to an isocyanate compound that is a carbon atom.
For example, a compound in which an isocyanate group is directly bonded to a tertiary carbon atom of a hydrocarbon constituting a chain structure, or a compound in which an isocyanate group is directly bonded to a tertiary carbon atom constituting an alicyclic structure is Corresponds to Group III isocyanate compound (A). Further, even if the molecule has an aromatic ring, if the isocyanate group is not directly connected to the aromatic ring and is directly connected to a tertiary carbon atom other than the aromatic ring, an aliphatic tertiary Corresponds to isocyanate compound (A).

The aliphatic tertiary isocyanate compound (A) may be any of a monoisocyanate compound, a diisocyanate compound, and an isocyanate compound having three or more isocyanate groups in one molecule.
When two or more isocyanate groups are present in one molecule, the aliphatic tertiary isocyanate compound (A) if at least one isocyanate group is directly bonded to a tertiary carbon atom other than the aromatic ring. It corresponds to. However, it is preferable that all isocyanate groups in one molecule are directly connected to a tertiary carbon atom other than the aromatic ring.
In the aliphatic tertiary isocyanate compound (A), the hydrocarbon moiety excluding the isocyanate group may or may not have a substituent other than the hydrocarbon group, and the substituent other than the hydrocarbon group. It is preferable not to have.

The aliphatic tertiary isocyanate compound (A) may or may not have a chain structure, may or may not have an alicyclic structure, and is aromatic. It may or may not have a ring.
The aliphatic tertiary isocyanate compound (A) is preferably one in which at least one aromatic ring is bonded to the tertiary carbon atom to which the isocyanate group is bonded. When the aromatic ring is bonded, the reason is not clear, but when the organic alkali metal (B) having Lewis basicity attacks the isocyanate group to form an intermediate, the intermediate is stabilized, and carbodiimidization proceeds. It is thought that it becomes easy.
In addition, when there are a plurality of tertiary carbon atoms to which an isocyanate group is bonded in one molecule, if at least one aromatic ring is bonded to at least one of the tertiary carbon atoms. Good. However, if there are multiple tertiary carbon atoms in one molecule to which an isocyanate group is bonded, at least one aromatic ring must be bonded to all the tertiary carbon atoms. Is preferred.

The aliphatic tertiary isocyanate compound (A) is preferably a compound represented by the following general formula (3).

In the formula (3), R ³ to R ⁵ are each independently a monovalent residue of any organic compound (provided that R ³ to R ⁵ are each independently a carbon atom in R ³ to R ⁵ , (Bonded to the carbon atom in (3)), preferably a substituted or unsubstituted hydrocarbon group, such as a substituted or unsubstituted alkyl group, alkenyl group, or aromatic group, such as an isocyanate. An alkyl group or an aromatic group that is not substituted with a group other than the group, that is, an alkyl group that is substituted or unsubstituted with an isocyanate group, or an aromatic group that is substituted or unsubstituted with an isocyanate group.
R ³ to R ⁵ may each independently have one or two or more isocyanate groups. One of R ³ to R ⁵ may have one or more isocyanate groups, and R ³ to R ⁵ may not have an isocyanate group.
R ³ to R ⁵ are not particularly limited, and may independently have, for example, 1 to 20 carbon atoms, for example 1 to 10 carbon atoms, or may have a larger carbon number.
Further, at least one of R ³ to R ⁵ is preferably a substituted or unsubstituted aromatic group. When it is a substituted or unsubstituted aromatic group, the reason is not clear, but when the organic alkali metal (B) having Lewis basicity attacks the isocyanate group to form an intermediate, the intermediate is stabilized, and carbodiimidization Is considered to be easier to proceed.
The substituted or unsubstituted aromatic group is preferably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and more preferably a substituted or unsubstituted phenyl group. The substituent in the substituted or unsubstituted aromatic group is preferably an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms or 2 carbon atoms. -4 alkenyl groups.

Examples of the compound represented by the general formula (3) include monoisocyanates such as 3-isopropenyl-α, α-dimethylbenzyl isocyanate (TMI); diisocyanates such as tetramethylxylylene diisocyanate (TMXDI).

When the aliphatic tertiary isocyanate compound (A) is a compound in which the isocyanate group is directly connected to the tertiary carbon atom of the hydrocarbon constituting the alicyclic structure, the alicyclic structure has an adamantane structure or a norbornane structure. , Norbornadiene structure, bicycloundecane structure, decahydronaphthalene structure, cubane structure, basketane structure, and Hausan structure. The alicyclic structure may or may not be bonded to a substituent other than an isocyanate group.

The aliphatic tertiary isocyanate compound (A) is preferably at least one of tetramethylxylylene diisocyanate (TMXDI) and 3-isopropenyl-α, α-dimethylbenzyl isocyanate (TMI), more preferably TMXDI or TMI, more preferably TMXDI.

When the aliphatic tertiary isocyanate compound (A) is a monoisocyanate compound, a decarboxylation condensation reaction of isocyanate groups of two monoisocyanate compounds is caused by the method for producing a carbodiimide compound according to the present embodiment, Carbodiimide compounds can be produced.

Further, when the aliphatic tertiary isocyanate compound (A) is a polyisocyanate compound, the monocarbodiimide compound is produced by polymerizing two polyisocyanate compounds by the method for producing a carbodiimide compound according to the present embodiment. In addition, three or more polyisocyanate compounds can be polymerized to produce a polycarbodiimide compound.

Here, the monoisocyanate compound means a compound having one isocyanate group. A polyisocyanate compound means a compound having two or more isocyanate groups. The phrase “isocyanate compound” is a concept including a monoisocyanate compound and a polyisocyanate compound.
The monocarbodiimide compound means a compound having one carbodiimide group. A polycarbodiimide compound means a compound having two or more carbodiimide groups. The phrase carbodiimide compound is a concept including a monocarbodiimide compound and a polycarbodiimide compound.

In the present embodiment, the degree of polymerization of the carbodiimide compound is P. The number of carbodiimide groups generated in one molecule of the carbodiimide compound when the carbodiimide compound is produced by the decarboxylation condensation reaction of the isocyanate compound. P is meant. For example, when P + 1 diisocyanate compounds are polymerized to produce a polycarbodiimide compound having P carbodiimide groups, the polymerization degree of the obtained carbodiimide compound is P. Even when P-1 diisocyanate compound and two monoisocyanate compounds are polymerized to produce a polycarbodiimide compound having P carbodiimide groups that are end-capped, the polymerization degree of the obtained carbodiimide compound Is P.
Moreover, in this Embodiment, NCO% in the carbodiimide compound produced by the carbodiimidization reaction of the aliphatic tertiary isocyanate compound (A) is the content of isocyanate groups (NCO groups) in the obtained carbodiimide compound ( Mass%). The NCO% can be measured by the method described in the examples.

<Organic alkali metal compound (B) having Lewis basicity>
The carbodiimidization catalyst used in the present embodiment is an organic alkali metal compound (B) having Lewis basicity. The organic alkali metal compound (B) having Lewis basicity used in this embodiment does not contain a phosphorus atom in the molecule. As a result, the organophosphorus compound remains in the obtained carbodiimide compound, and when it is used as an additive, it interferes with the counterpart material, making it difficult to use, and the trouble of removing the remaining organophosphorus compound. It is avoided that it occurs.

The addition amount of the organic alkali metal compound (B) having Lewis basicity may be 0.01 parts by mass or more with respect to 100 parts by mass of the aliphatic tertiary isocyanate compound (A), and there is no particular upper limit. It is preferable that it is 0.01 mass part or more and 5 mass parts or less. If it is 0.01 mass part or more, it is excellent in the promotion effect of a carbodiimide reaction, and if it exceeds 5 mass parts, the promotion effect of a carbodiimide reaction will not fully improve even if it adds more. From this viewpoint, the addition amount is more preferably 0.05 to 3 parts by mass, and still more preferably 0.1 to 1 part by mass.

The organic alkali metal compound (B) having Lewis basicity is preferably at least one of a metal alkoxide, a metal amide, and a metal carboxylate, and in one embodiment, is a metal amide.

≪Metal alkoxide≫
The metal alkoxide is an alkali metal alkoxide.
The alkali metal alkoxide is preferably a compound represented by the following general formula (5).

M-OR ¹⁰ (5)
In formula (5), M is an alkali metal, and preferably at least one of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). More preferably, it is at least one of lithium (Li), sodium (Na), cesium (Cs) and potassium (K), more preferably lithium (Li), sodium (Na), and potassium (K). At least one of the following.
In the formula (5), R ¹⁰ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. An alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 2 to 4 carbon atoms, still more preferably an ethyl group and At least one tert-butyl group.
It is.

The alkali metal alkoxide is preferably at least one of potassium tert-butoxide, sodium tert-butoxide, potassium ethoxide and sodium ethoxide, more preferably at least one of potassium tert-butoxide and sodium ethoxide.

≪Metal amide≫
The metal amide is preferably an alkali metal amide such as lithium amide, sodium amide, potassium amide or cesium amide, more preferably lithium amide, and still more preferably lithium diisopropylamide (LDA).

≪Metal carboxylates≫
The metal carboxylate is preferably an alkali metal acetate, more preferably at least one of potassium acetate and cesium acetate.

Moreover, in the organic alkali metal compound (B) having Lewis basicity, the suitable type of the organic compound that binds to the alkali metal varies depending on the type of the alkali metal.
That is, when the alkali metal is lithium, sodium, or potassium, the organic alkali metal compound (B) having Lewis basicity is preferably a metal alkoxide, a metal amide, and a metal carboxyl from the viewpoint of handleability and stability. At least one acid salt, more preferably at least one metal alkoxide and metal amide.
In addition, when the alkali metal is cesium, the organic alkali metal compound (B) having Lewis basicity is preferably at least one of cesium alkoxide, cesium amide, and cesium carboxylate from the viewpoints of handleability and stability. Yes, more preferably cesium carboxylate.

<Phase transfer catalyst (C)>
In the carbodiimide production step, the aliphatic tertiary isocyanate compound (A) may be reacted in the presence of the Lewis alkali basic organic alkali metal compound (B) and the phase transfer catalyst (C). Thereby, a carbodiimide compound can be obtained more rapidly.
In the present embodiment, the “phase transfer catalyst” is a reagent used for reacting an organic compound insoluble in water and a compound insoluble in an organic solvent, and more specifically, a tertiary isocyanate group-containing compound. It is a reagent used to efficiently react (A) with an organic alkali metal compound (B) having Lewis basicity.

The amount of the phase transfer catalyst (C) added may be 0.01 parts by mass or more with respect to 100 parts by mass of the aliphatic tertiary isocyanate compound (A), and there is no particular upper limit. When it is 0.01 part by mass or more, the effect of promoting the carbodiimide reaction is excellent, and when it is 300 parts by mass or more, the effect of promoting the carbodiimide reaction is not sufficiently improved even if it is added more. From this viewpoint, the amount added is more preferably 0.01 to 300, still more preferably 0.05 to 200 parts by mass, and still more preferably 0.1 to 100 parts by mass. In addition, when reducing the addition amount of a phase transfer catalyst (C), even if it is 10 mass parts or less, for example, 5 mass parts or less, the said effect can be show | played.

The phase transfer catalyst (C) used in the present embodiment is not particularly limited, but is preferably at least one of a crown ether, a quaternary ammonium salt, and a polyalkylene glycol dialkyl ether, more preferably a crown ether. , A quaternary ammonium salt, and at least one compound represented by the following general formula (1).
Among these, crown ether is more preferable from the viewpoint of improving the reaction rate, and at least one of quaternary ammonium salt and polyalkylene glycol dialkyl ether is more preferable from the viewpoint of economy.

≪Crown ether≫
The crown ether is not particularly limited, and may be a narrowly defined crown ether represented by the general structural formula (—CH ₂ —CH ₂ —O—) _n (n is an integer), and oxygen constituting the ring of the crown ether A thiacrown ether in which part or all of the atoms are substituted with sulfur atoms may be used, or an azacrown ether in which some or all of the oxygen is substituted with NR (R is a substituent) or the like . These crown ethers may be modified. For example, an unmodified narrow-sense crown ether may be used.

The crown ether is preferably 4′-acetylbenzo-15-crown 5-ether, 4′-acetylbenzo-18-crown 6-ether (4′-acetylbenzo-15-crown 5-ether). -18-crown 6-Ether), 4′-Aminobenzo-15-crown 5-ether, 1-aza-12-crown 4-ether (1-Aza-12) -crown 4-Ether), 1-aza-15-crown 5-ether, 1-aza-18-crown 6-ether (1-Aza-18-crown 6-ether) Ether), benzo-12-crown 4-ether, benzo-15-crown 5-ether, benzo-18-crown 6-ether ( Benzo-18-crown 6-Ether), bis (1,4-phenylene) -34-crown 10-ether (Bis (1,4-phenylene) -34-crown 10-E ther), 4'-Bromobenzo-15-crown 5-ether, 4'-Bromobenzo-18-crown 6-ether (4'-Bromobenzo-18-crown 6-ether) Ether), 4'-Carboxybenzo-15-crown 5-Ether, 4'-Carboxybenzo-18-crown 6-ether (4'-Carboxybenzo-18-crown) 6-Ether), 15-crown 4 [4- (2,4-dinitrophenylazo) phenol] (15-Crown-4 [4- (2,4-Dinitrophenylazo) phenol]), 18-crown 5 [4- (2,4-Dinitrophenylazo) phenol] (18-Crown-5 [4- (2,4-Dinitrophenylazo) phenol]), 12-Crown 4-Ether, 15-Crown 5 -Ether (15-Crown 5-Ether), 18-Crown 6-Ether, 24-Crown 8-Ether (24-Crown 8-Ether) ther), 4,10-diaza-12-crown 4-ether (4,10-Diaza-12-crown 4-Ether), 4,10-diaza-15-crown 5-ether (4,10-Diaza-15) -crown 5-Ether), 4,13-Diaza-18-crown 6-ether (4,13-Diaza-18-crown 6-Ether), Dibenzo-15-crown 5-ether (Dibenzo-15-crown 5-ether) Ether), dibenzo-18-crown 6-ether (Dibenzo-18-crown 6-Ether), dibenzo-21-crown 7-ether, dibenzo-24-crown 8-ether ( Dibenzo-24-crown 8-Ether), Dibenzo-30-crown 10-Ether, N, N′-Dibenzyl-4,13-diaza-18-crown 6-ether (N , N'-Dibenzyl-4,13-diaza-18-crown 6-Ether), Dicyclohexano-18-crown 6-Ethe r) 4'-Formylbenzo-15-crown 5-ether, 4'-Formylbenzo-15-crown 5-ether 6-Ether), 1,4,7,10,13,16-hexaazacyclooctadecane (1,4,7,10,13,16-Hexaazacyclooctadecane), 1,4,7,10,13,16-hexa Azacyclooctadecane hexahydrochloride (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane) (4,7,13,16,21,24-Hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane), 2- (hydroxymethyl) -12-crown 4-ether (2- (Hydroxymethyl) -12- crown 4-Ether), 2- (hydroxymethyl) -15-crown 5-ether (2- (Hydroxymethyl) -15-crown 5-Ether), 2 -(Hydroxymethyl) -18-crown 6-ether (2- (Hydroxymethyl) -18-crown 6-Ether), 4'-Methoxycarbonylbenzo-15-crown 5 -Ether), 4'-Nitrobenzo-15-crown 5-ether, 4'-Nitrobenzo-18-crown 6-ether (4'-Nitrobenzo-18-crown 6) -Ether), N-Phenylaza-15-crown 5-ether, 1,4,7,10-tetraazacyclododecane (1,4,7,10-Tetraazacyclododecane) 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetraacetic Acid) , 7,10-Tetraazacyclododecane Tetrahydrochloride (1,4,7,10-Tetraazacyclododecane Tetrahydrochloride), 1,4,8,12-Te Laazacyclopentadecane (1,4,8,12-Tetraazacyclopentadecane), 1,4,8,11-tetraazacyclotetradecane (1,4,8,11-Tetraazacyclotetradecane), 1,4,7,10-tetrabenzyl -1,4,7,10-tetraazacyclododecane (1,4,7,10-Tetrabenzyl-1,4,7,10-tetraazacyclododecane), tetraethyl-1,4,8,11-tetraazacyclotetradecane 1,4,8,11-tetraacetate (1,4,8,11-Tetraazacyclotetradecane-1,4,8,11-tetraacetate), 1,4,8,11-tetramethyl-1,4,8 , 11-Tetraazacyclotetradecane (1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane), 1,4,8,11-tetrathiacyclotetradecane (1,4,8,11- Tetrathiacyclotetradecane), 1,5,9-triazacyclododecane (1,5,9-Triazacyclododecane), 1,4,7-triazashi Rononane (1,4,7-Triazacyclononane), 1,4,7-Triazacyclononane trihydrochloride (1,4,7-Triazacyclononane Trihydrochloride), Tri-tert-butyl-1,4,7,10-tetra Azacyclododecane-1,4,7,10-tetraacetate (Tri-tert-butyl 1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetraacetate), tri-tert-butyl-1,4 , 7,10-Tetraazacyclododecane-1,4,7-triacetate (1,4,7-triacetate), 1,4,7-triacetate 1,4,7-triazacyclononane (NaHCO ₃ stabilized) (1,4,7-Trimethyl-1,4,7-triazacyclononane (stabilized with NaHCO ₃ )), 1,4,7-trithiacyclononane It is at least one of (1,4,7-Trithiacyclononane).

Among these, more preferred is at least one of 12-crown 4-ether, 15-crown 5-ether, 18-crown 6-ether, and 24-crown 8-ether, and even more preferred is 18-crown 6 -Ether, 15-crown 5-ether.
The crown ether is preferably selected as appropriate according to the kind of cation in the organic alkali metal compound (B) having Lewis basicity. For example, 18-crown 6-ether is preferred when the cation is potassium (K), and 15-crown 5-ether is preferred when the cation is sodium (Na).

≪Quaternary ammonium salt≫
The quaternary ammonium salt is not particularly limited, but preferably tetrabutylammonium bromide (Tetrabutylammonium Bromide), tetrabutylammonium iodide (Tetrabutylammonium Iodide), tetrabutylammonium 2-ethylhexanoate , Tetrabutylammonium Hydrogen Sulphate, Tetrabutylammonium Chloride, Tetrabutylammonium fluoride trihydrate, Tetrabutylammonium nitrate Tetrabutylammonium nitrate Tetrabutylammonium nitrite, Tetrabutylammonium Acetate, Tetrabutylammonium Triiodide, Tetrae Tetraethylammonium Bromide, Tetraethylammonium Chloride, Tetraethylammonium fluoride dihydrate, Tetrapropylammonium bromide, Tetrapropylammonium Chloride, Tetramethyl Ammonium chloride (Tetramethylammonium Chloride), Benzyltriethylammonium Chloride (Benzyltrimethylammonium Chloride), Benzyltrimethylammonium Chloride, Benzyltrimethylammonium Chloride, Benzyltrimethylammonium Bromide, Trimethylammonium Dichloroiodate (Benzyltrimethylamm onium Dichloroiodate, Benzyltributylammonium Chloride, Benzyltributylammonium Bromide, Methyltributylammonium Chloride, Methyltributylammonium Bromide, Methyltributylammonium Chloride, Methyltriethylammonium Chloride Methyltriethylammonium Bromide, Phenyltrimethylammonium chloride, Behentrimonium Chloride, Cetyltrimethylammonium Bromide, Cetyltrimethylammonium Bromide, Cetyltrimethylammonium Chloride, Cetyltrimethylammonium Chloride Hydrogen salt (Cetyltrimethylammonium Hydrogen Sulphate), Cetyldimethylethylammonium Bromide (Cetyldimethylethylammonium Bromide), Cetyldimethylethylammonium Bromide (Cetyldimethylethylammonium Bromide), Cetimide , Didecyldimethylammonium chloride, Dodecyltrimethylammonium Chloride, Dodecyltrimethylammonium Bromide, Myristyltrimethylammonium Bromide, Methyltrioctylammonium chloride (Methyl-trimethylammonium chloride) n-octylammonium bromide (Tetra-n-octylammonium Bromide Is at least one of trimethyl -n- octyl ammonium bromide (Trimethyloctylammonium bromide), and trioctyl methyl ammonium bromide (Trioctyl methyl ammonium bromide).

Among these, from the viewpoint of availability, a tetrabutylammonium salt is preferable, for example, tetrabutylammonium 2-ethylhexanoate.

≪Polyalkylene glycol dialkyl ether≫
The polyalkylene glycol dialkyl ether is not particularly limited, but is preferably a compound represented by the following general formula (1).

In the formula (1), X and Y are each independently a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group. R ¹ is an alkylene group having 2 to 3 carbon atoms. m is an integer of 2 to 500, preferably an integer of 3 to 300, and more preferably an integer of 4 to 200.
The compound represented by the formula (1) is preferably at least one of polyoxyethylene dialkyl ether and polyoxypropylene dialkyl ether.
The polyoxyethylene dialkyl ether is preferably at least one of polyoxyethylene dimethyl ether, polyoxyethylene diethyl ether, polyoxyethylene dipropyl ether, polyoxyethylene dibutyl ether, and polyoxyethylene diphenyl ether.
The polyoxypropylene dialkyl ether is preferably at least one of polyoxypropylene dimethyl ether, polyoxypropylene diethyl ether, polyoxypropylene dipropyl ether, polyoxypropylene dibutyl ether, and polyoxypropylene diphenyl ether.
The number average molecular weight of the polyalkylene glycol dialkyl ether is preferably 100 or more from the viewpoint of improving the reaction rate of the carbodiimidization reaction of the tertiary isocyanate group-containing compound (A), and from the viewpoint of handleability and solubility. , Preferably 5000 or less. From the same viewpoint, the number average molecular weight is more preferably 100 to 1000, still more preferably 100 to 800, still more preferably 200 to 700, still more preferably 250 to 700, and still more preferably 300 to 600. .

<Other ingredients>
In the carbodiimide production step, components other than those described above may be added.
For example, an organic solvent may be added. Examples of the organic solvent include ethylene glycol monomethyl ether acetate (118.13), diethylene glycol dimethyl ether (134.18), dipropylene glycol dimethyl ether (162.23), diethylene glycol ethyl methyl ether (148.20), diethylene glycol isopropyl methyl ether (162). .23), diethylene glycol diethyl ether (162.23), diethylene glycol butyl methyl ether (176.26), tripropylene glycol dimethyl ether (206.28), triethylene glycol dimethyl ether (178.23), diethylene glycol dibutyl ether (218.34). ), Triethylene glycol butyl methyl ether (220.31), tetraethylene No glycol dimethyl ether (222.28) active hydrogen groups such as, high organic solvent is preferably a boiling point above the temperature of the synthesis. Thereby, when the reaction rate of carbodiimidization reaction improves, the viscosity adjustment of the obtained polycarbodiimide becomes easy. The numbers in parentheses indicate the molecular weight.
The amount of other components added is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 10 parts by mass or less with respect to 100 parts by mass of the tertiary isocyanate group-containing compound (A).

<Reaction conditions>
In the carbodiimide production step, the reaction temperature is appropriately set according to the type of the aliphatic tertiary isocyanate compound (A).
The reaction temperature is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 100 ° C. or higher, and preferably when the decomposition temperature of the aliphatic tertiary isocyanate compound (A) is X ° C. Is X ° C. or lower, more preferably X-5 ° C. or lower, and still more preferably X-10 ° C. or lower.

For example, when the aliphatic tertiary isocyanate compound (A) is at least one of tetramethylxylylene diisocyanate and 3-isopropenyl-α, α-dimethylbenzyl isocyanate, the reaction temperature is preferably 80 to 200 ° C., More preferably, it is 100 to 190 ° C, and further preferably 130 to 180 ° C.
The reaction atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The inert gas may be sealed by a flow method or a bubbling method in which the gas is sealed in a liquid.

[Sealing process]
The method for producing carbodiimide according to the present embodiment is based on the aliphatic tertiary isocyanate compound (A) at least one time point among the three time points before, during and after the carbodiimide production step. You may have the sealing process which makes a part of isocyanate group react with sealing agent.
The degree of polymerization of the obtained carbodiimide compound can be controlled by the sealing step.
As the sealing agent, any organic compound having a functional group that reacts with the terminal isocyanate group of the carbodiimide compound may be used. Examples of the organic compound having a functional group that reacts with an isocyanate group include compounds having active hydrogen such as alcohols, amines, and carboxylic acids, compounds having a monoisocyanate group, compounds represented by the general formula (2-1) described later ( D-1), and the compound (D-1) represented by the general formula (2-1) described later is preferable.
The sealing step may be performed at least one time point among the three time points before, during and after the carbodiimide generation step, and only at any one time point. For example, you may implement before a production | generation process.
In the sealing step, a part of the end of the aliphatic tertiary isocyanate compound (A) is sealed with a sealant. Thus, the carbodiimide compound by which the terminal was sealed can be manufactured by using the aliphatic tertiary isocyanate compound (A) by which the terminal part was sealed for a carbodiimide production | generation process. Moreover, the polymerization degree of the carbodiimide compound obtained can be controlled. As the aliphatic tertiary isocyanate compound (A), an aliphatic tertiary isocyanate compound (A) in which a part of the terminal isocyanate group is previously sealed is used, and the sealing step is omitted. Good.

<Compound (D-1) Represented by General Formula (2-1)>
The compound (D-1) used in the present embodiment is represented by the following general formula (2-1).

In the formula (2-1), Z represents a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group. R ² is an alkylene group having 2 to 3 carbon atoms. n is an integer of 2 to 500, preferably an integer of 3 to 300, and more preferably an integer of 4 to 200.
The compound (D-1) represented by the formula (2-1) is preferably at least one of polyoxyethylene monoalkyl ether and polyoxypropylene monoalkyl ether.
The polyoxyethylene monoalkyl ether is preferably at least one of polyoxyethylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monopropyl ether, polyoxyethylene monobutyl ether, and polyoxyethylene monophenyl ether .
The polyoxypropylene monoalkyl ether is preferably at least one of polyoxypropylene monomethyl ether, polyoxypropylene monoethyl ether, polyoxypropylene monopropyl ether, polyoxypropylene monobutyl ether, and polyoxypropylene monophenyl ether. It is.
When the compound (D-1) is used as an end-capping agent, a urethanization reaction between a part of the isocyanate group in the aliphatic tertiary isocyanate compound (A) and the hydroxyl group of the compound (D-1) causes a fat A part of the terminal of the group tertiary isocyanate compound (A) is sealed. In this way, a part of the end of the aliphatic tertiary isocyanate compound (A) is sealed with the compound (D-1) and then subjected to a carbodiimide production step, whereby the residue of the compound (D-1) is transferred between phases. It works in the same way as a catalyst and improves the reaction rate of the carbodiimidization reaction.
The sealing of the aliphatic tertiary isocyanate compound (A) with this compound (D-1) is at least one time point before the carbodiimide production step, during the production step, and after the production step. However, it is preferably performed before the production step.
The number average molecular weight of the compound (D-1) is preferably 100 or more from the viewpoint of improving the reaction rate of the carbodiimidization reaction of the tertiary isocyanate group-containing compound (A), and from the viewpoints of handleability and solubility. Therefore, it is preferably 5000 or less. From the same viewpoint, the number average molecular weight is more preferably 100 to 1000, still more preferably 100 to 800, still more preferably 200 to 700, still more preferably 250 to 700, and still more preferably 300 to 600. .

The amount of compound (D-1) added can be appropriately selected according to the degree of polymerization of the carbodiimide compound to be produced.
However, the amount of the compound (D-1) added is preferably 0.01 parts by mass or more, more preferably 100 parts by mass with respect to 100 parts by mass of the aliphatic tertiary isocyanate compound (A) from the viewpoint of promoting the carbodiimide reaction. Is 0.1 part by mass or more, more preferably 1.0 part by mass or more. The amount of the compound (D-1) added is preferably 200 parts by mass or less with respect to 100 parts by mass of the aliphatic tertiary isocyanate compound (A) from the economical viewpoint and the viewpoint of securing the carbodiimide concentration. More preferably, it is 50 mass parts or less, More preferably, it is 5.0 mass parts or less.

<Reaction conditions>
In the sealing step, the reaction temperature is appropriately set according to the type of the aliphatic tertiary isocyanate compound (A).
The reaction temperature is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 100 ° C. or higher, and preferably when the decomposition temperature of the aliphatic tertiary isocyanate compound (A) is X ° C. Is X ° C. or lower, more preferably X-5 ° C. or lower, and still more preferably X-10 ° C. or lower.
Moreover, you may make it react at a still lower temperature using a urethanization catalyst as needed.

[Chain extension process]
The method for producing carbodiimide according to the present embodiment includes the aliphatic tertiary isocyanate compound (A) at least one time point among the three time points before the carbodiimide production step, during the production step, and after the production step. It may have a chain extension step of reacting a part of the isocyanate group in the carbodiimide compound obtained by the reaction of) with a chain extender. However, the chain extension step may not be performed.
The chain extender may be any organic compound having two or more functional groups that react with the terminal isocyanate group of the carbodiimide compound. The organic compound is preferably a polyol having two or more hydroxyl groups or a polyamine having two or more amino groups, more preferably a diol or diamine, and a compound represented by the general formula (2-2) (D-2) described later. Is more preferable.
The chain extension step may be performed before the carbodiimide generation step, during the generation step, and at least one time point among the three time points after the generation step, and only at any one time point. You may implement, for example after a production | generation process.
The degree of polymerization of the resulting carbodiimide compound can be controlled by the chain extension step. However, the chain extension step may be omitted.

<Compound (D-2) Represented by General Formula (2-2)>
The compound (D-2) used in the present embodiment is represented by the following general formula (2-2).

In the formula (2-2), R ³ is an alkylene group having 2 to 3 carbon atoms. p is an integer of 2 to 500.
When the compound (D-2) is used as a chain extender, a urethanization reaction between a part of the isocyanate group in the aliphatic tertiary isocyanate compound (A) and a hydroxyl group of the chain extender (D-2) A part of the terminal of the aliphatic tertiary isocyanate compound (A) is chain-extended. Thus, in the substituent-containing aliphatic tertiary isocyanate compound in which a part of the terminal is chain-extended with the chain extender (D-2), the residue of the compound (D-2) functions as a phase transfer catalyst. The reaction rate of the carbodiimidization reaction is improved.
The compound (D-2) is preferably at least one of polyoxyethylene and polyoxypropylene.
The chain extension with the compound (D-2) may be performed at least one time point among the three time points before, during and after the carbodiimide production step. It may be carried out at only one point in time, for example after the production step.
The number average molecular weight of the compound (D-2) is preferably 100 or more from the viewpoint of improving the reaction rate of the carbodiimidization reaction of the tertiary isocyanate group-containing compound (A), and from the viewpoints of handleability and solubility. Therefore, it is preferably 5000 or less. From the same viewpoint, the number average molecular weight is more preferably 100 to 1000, still more preferably 100 to 800, still more preferably 200 to 700, still more preferably 250 to 700, and still more preferably 300 to 600. .

The amount of compound (D-2) added can be appropriately selected according to the degree of polymerization of the carbodiimide compound to be produced.
However, when the compound (D-2) is added, the addition amount is preferably 0.01 mass with respect to 100 mass parts of the aliphatic tertiary isocyanate compound (A) from the viewpoint of promoting the carbodiimide reaction. Part or more, more preferably 0.1 part by weight or more, still more preferably 1.0 part by weight or more. Further, the amount of the compound (D-2) added is preferably 200 parts by mass or less with respect to 100 parts by mass of the aliphatic tertiary isocyanate compound (A) from the economical viewpoint and the viewpoint of securing the carbodiimide concentration. More preferably, it is 50 mass parts or less, More preferably, it is 5.0 mass parts or less.

<Reaction conditions>
In the chain extension step, the reaction temperature is appropriately set according to the type of the aliphatic tertiary isocyanate compound (A). The details of the reaction conditions are the same as in the sealing step.

[Adsorption removal process]
The method for producing a carbodiimide in the present embodiment uses an adsorbent (E) in the middle or after the carbodiimide production step, preferably after the carbodiimide production step, and uses the Lewis basic organic alkali metal compound ( You may have the adsorption removal process of adsorbing and removing B). Thereby, the organic alkali metal compound (B) having Lewis basicity can be sufficiently removed from the obtained carbodiimide compound. However, the adsorption removal step may be omitted.
Since the organic alkali metal compound (B) may be colored when used in combination with an antioxidant, the content of the organic alkali metal compound (B) in the carbodiimide compound is preferably 2000 ppm by mass or less. More preferably, it is 1000 mass ppm or less, More preferably, it is 200 mass ppm or less.
The adsorption method may be a stirring and mixing method in which the adsorbent is mixed with the carbodiimide compound and then filtered, or a filtration layer method in which the carbodiimide compound is distributed in the filtration layer filled with the adsorbent. It is not necessary.

<Adsorbent (E)>
The adsorbent (E) used in the present embodiment is not particularly limited, but is preferably a synthetic aluminum silicate-based adsorbent, synthetic magnesium silicate, acidic cation exchange resin, basic anion exchange resin, alumina. , Silica gel type adsorbent, zeolite type adsorbent, hydrotalcite, magnesium oxide-aluminum oxide solid solution, aluminum hydroxide, magnesium oxide, and aluminum hydroxide-sodium hydrogen carbonate coprecipitate (dorsonite). More preferably, at least one of a synthetic aluminum silicate adsorbent, a synthetic magnesium silicate adsorbent, an acidic cation exchange resin, a basic anion exchange resin, alumina, a silica gel adsorbent, and a zeolite adsorbent It is.
The blending amount of the adsorbent (E) is preferably 50 to 5000 parts by mass, more preferably 100 to 1000 parts by mass, and still more preferably 200 parts per 100 parts by mass of the organic alkali metal compound (B) having Lewis basicity. Up to 1000 parts by mass, more preferably 400 to 800 parts by mass.

<Carbodiimide compound>
According to the method for producing a carbodiimide compound according to the present embodiment, even when an organophosphorus compound is not substantially used as a carbodiimidization catalyst, an aliphatic tertiary isocyanate compound is reacted to increase the carbodiimide compound. It can be produced in a yield.
The carbodiimide compound obtained by the method for producing a carbodiimide compound according to the present embodiment preferably has a purity (content) of 90% by mass or more and does not contain phospholene oxides or phospholene oxides. Content is 1 mass ppm or less.
Here, the purity (content) means the content of the carbodiimide compound in the active ingredient of the product obtained by the method for producing the carbodiimide compound according to the present embodiment. Here, the active ingredient means the total amount of the components excluding the solvent when the product contains a solvent, and means the total amount of the product when the product does not contain a solvent. The same applies to the stabilizer and carbodiimide composition described later.
The carbodiimide compound according to the present embodiment can be suitably used for preventing hydrolysis of the resin. Here, examples of the resin include thermoplastic polyurethane and the like, which can be added and stored in advance to diisocyanate, which is a raw material of urethane resin, and a process of adding a stabilizer after the urethane resin is manufactured. And can be used for the production of a urethane resin containing a stabilizer.

2. Stabilizer The stabilizer according to the present embodiment includes a carbodiimide compound having an aliphatic tertiary isocyanate compound (A) as a constituent unit and an alkali metal (an alkali alkali compound derived from an organic alkali metal compound (B) having Lewis basicity). Metal) and no phospholene oxides or a phospholene oxide content of 1 mass ppm or less.

The stabilizer is useful as a stabilizer for various resins such as thermoplastic resins and as a hydrolysis inhibitor. In addition, it can be added and stored in advance to diisocyanate, which is a raw material of urethane resin, and it is useful for the production of urethane resin containing stabilizer without going through the process of adding stabilizer to urethane resin. is there. Here, the resin is not particularly limited, and examples thereof include polyurethane and thermoplastic polyurethane.

As the aliphatic tertiary isocyanate compound (A) which is a structural unit of the carbodiimide compound contained in the stabilizer, the same as those used in the above-mentioned “1. Production method of carbodiimide compound” is preferable. It is.
Moreover, as described in the above-mentioned “1. Production method of carbodiimide compound”, the carbodiimide compound may be sealed with a sealing agent. As the sealant, the above-mentioned compound (D-1) is suitable.
Moreover, as described in the above-mentioned “1. Method for producing carbodiimide compound”, the carbodiimide compound may be sealed with a chain extender. As the chain extender, the aforementioned compound (D-2) is preferable.
The content (that is, purity) of the carbodiimide compound having the aliphatic tertiary isocyanate compound (A) as a constituent unit in the stabilizer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably. It is 95 mass% or more, More preferably, it is 99 mass%.

The alkali metal contained in the stabilizer is preferably at least one of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). , More preferably at least one of lithium (Li), sodium (Na), cesium (Cs), and potassium (K), and more preferably at least one of lithium (Li), sodium (Na), and potassium (K). One type.
The alkali metal content in the stabilizer is preferably less than 2000 ppm by mass. If it is less than 2000 ppm by mass, the problem that it becomes difficult to use due to interference with the mating material is prevented.
Further, the content of alkali metal in the stabilizer is preferably 10 ppm by mass or more, more preferably 100 ppm by mass or more, from the viewpoint of ease of production.

The stabilizer preferably does not contain phospholene oxides or the content of phospholene oxides is 1 ppm by mass or less.
This prevents the problem that the phospholene oxides interfere with the counterpart material and become difficult to use.

The stabilizer may further contain a phase transfer catalyst (C).
The content of the phase transfer catalyst (C) in the stabilizer is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and still more preferably 0 to 100 parts by mass of the carbodiimide compound. .5 to 2 parts by mass. When it is 10 parts by mass or less, when used as a stabilizer for various resins, occurrence of defects such as poor appearance due to bleed-out of the phase transfer catalyst and stickiness during use is prevented, and 0.1 parts by mass or more When it is, the target reaction promotion effect is favorable.

The said stabilizer is suitably manufactured by the manufacturing method containing the above-mentioned "1. the manufacturing method of a carbodiimide compound."
That is, the stabilizer may be produced only by the above-mentioned “1. Production method of carbodiimide compound”, and may be produced through other steps such as adding other additives thereafter.

3. Carbodiimide Composition The carbodiimide composition according to the present embodiment is derived from a carbodiimide compound having an aliphatic tertiary isocyanate compound (A) as a structural unit and an alkali metal (an organic alkali metal compound (B) having Lewis basicity). A carbodiimide composition containing no phospholene oxides or having a phospholene oxide content of 1 ppm by mass or less.
Each component in the carbodiimide composition is the same as the stabilizer described above.

4). The method for producing polyurethane according to the present embodiment is a method for producing polyurethane, in which polyurethane, preferably thermoplastic polyurethane, is obtained by reacting polyol and diisocyanate in the presence of a stabilizer. The stabilizer is a method for producing polyurethane, which contains an aliphatic tertiary carbodiimide derived from an aliphatic tertiary isocyanate compound and has an alkali metal content of less than 2000 ppm by mass.
The blending amount of the aliphatic tertiary carbodiimide derived from the aliphatic tertiary isocyanate compound with respect to 100 parts by mass of the total amount of the polyol and the diisocyanate is preferably 0.1 to 2 parts by mass, more preferably 0. .5 to 1 part by mass.
The aliphatic tertiary carbodiimide derived from the aliphatic tertiary isocyanate compound is preferably 20 to 50 ° C., particularly preferably 25 to 35 ° C., in liquid form, continuously or batchwise. It is preferable to be metered.
As the stabilizer, those described in “2. Stabilizer” are preferably used.

A method for producing a polyurethane according to another embodiment of the present invention is a method for producing a polyurethane, preferably a polyurethane, preferably a thermoplastic polyurethane, by reacting a polyol and a diisocyanate in the presence of a stabilizer. Is a method for producing polyurethane, which is a carbodiimide compound produced by the method for producing a carbodiimide compound according to the above-described embodiment.

5. Ester resin composition The ester resin composition according to the present embodiment is an ester resin composition including the carbodiimide composition and the ester resin.
The content of the carbodiimide composition in the ester resin composition is 0.2 to 5.0 parts by mass with respect to 100 parts by mass of the ester resin.

Further, an ester resin composition according to another embodiment of the present invention is an ester resin composition containing the above-described stabilizer and an ester resin. The content of the stabilizer in the ester resin composition is preferably 0.2 to 5.0 parts by mass with respect to 100 parts by mass of the ester resin.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this.
In addition, each evaluation in the following examples was performed according to the following method.
(1) Infrared absorption (IR) spectrum measurement FTIR-8200PC (manufactured by Shimadzu Corporation) was used.
(2) GPC
RI detector: RID-6A (manufactured by Shimadzu Corporation)
Column: KF-806, KF-804L, KF-804L (manufactured by Showa Denko KK)
Developing solvent: tetrahydrofuran (THF) 1 ml / min.
The number average molecular weight (Mn) was calculated by polystyrene conversion.
(3) NCO%
Using Hiranuma automatic titrator COM-900 (Hiranuma Sangyo Co., Ltd.) and Tight Station K-900 (Hiranuma Sangyo Co., Ltd.), a dibutylamine / toluene solution with a known concentration was added, and calculated by potentiometric titration with aqueous hydrochloric acid. .
(4) Confirmation of the presence or absence of a carbodiimidization catalyst 10 g of diphenylmethane diisocyanate and 1 g of the obtained polycarbodiimide are mixed, heated at 100 ° C. for 1 hour with stirring, and then mixed immediately after mixing by infrared absorption (IR) spectrum measurement. Absorption peak after heating was confirmed, and it was derived from the nurate compound of diphenylmethane diisocyanate (wavelength around 1710 cm ⁻¹ and wavelength around 1411 cm ⁻¹ ), whether or not a peak was generated, derived from a carbodiimide compound (wavelength around 2138 cm ⁻¹ and wavelength 2112 cm ^−1). Before and after) The presence or absence of a carbodiimidization catalyst was confirmed by the presence or absence of a peak.

(Alkali metal determination)
The alkali metal contained in the carbodiimide compound and the stabilizer was quantified by the following operation by high frequency inductively coupled plasma (ICP) emission spectroscopy.
A carbodiimide compound or 1.00 g of stabilizer and 19.00 g of ultrapure water were mixed and allowed to stand for 24 hours, and then the mixed aqueous solution was filtered using a 0.1 μm membrane filter. Elemental analysis of the filtrate thus obtained was performed using a high frequency inductively coupled plasma (ICP) emission spectroscopic analyzer (product name: ICPS-8100, Shimadzu Corporation). Based on the difference calculated from the results of the obtained elemental analysis and the measurement result of only ultrapure water, the content of each alkali metal atom in the carbodiimide compound or the stabilizer was determined from the calibration curve of each alkali metal.

Example 1
100 g of tetramethylxylylene diisocyanate and 0.5 g of Lewis alkali basic organic alkali metal (potassium tert-butoxide) as a carbodiimidization catalyst are placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, and stirred at 175 ° C. in a nitrogen stream. The reaction was continued until the NCO% measurement result was 3.74%. The synthesis time (time required for carbodiimidization) was 26 hours.
The value of NCO% is 3.74% when 11 tetramethylxylylene diisocyanate is decarboxylated and condensed to produce a carbodiimide compound having a polymerization degree of 10 (both ends are NCO groups). Is the content (% by mass) of the NCO group in the carbodiimide compound. The said reaction was implemented until the measured value of NCO% reached the said target value for the said value 3.74% as the target value.

As a result of analyzing the obtained isocyanate-terminated polytetramethylxylylene carbodiimide (average polymerization degree = 10), an absorption peak due to a carbodiimide group having a wavelength of about 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement.
The absorption wavelength due isocyanurates an isocyanate trimer, wavelength 1710 cm ^-1 longitudinal and wavelength 1411Cm ^-1 before and after the absorption peak, the absorption wavelength due uretdione an isocyanate dimer, wavelength 1765Cm ^-1 longitudinal and wavelength 1410cm An absorption peak around ⁻¹ and an absorption peak based on other by-products could not be confirmed. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 1891.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.
The raw material composition and synthesis conditions are shown in Table 1, and the evaluation results are shown in Table 2. The same applies to the following examples and comparative examples.

Example 2
100 g of 3-isopropenyl-α, α-dimethylbenzyl isocyanate and 0.5 g of Lewis alkali basic organic alkali metal (potassium tert-butoxide) as a carbodiimidization catalyst were placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer. The mixture was stirred under a nitrogen stream at 175 ° C., and the reaction was carried out until the absorption of isocyanate groups having a wavelength of 2200 to 2300 cm ⁻¹ disappeared (until NCO% became 0%) by infrared absorption (IR) spectrum measurement. The synthesis time was 45 hours. As a result of analyzing the obtained di (3-isopropenyl-α, α-dimethylbenzyl) monocarbodiimide, an absorption peak due to a carbodiimide group having a wavelength of around 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, as well as other absorption peak based on by-products Could not be confirmed. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 145.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.

Example 3
100 g of tetramethylxylylene diisocyanate and 0.5 g of an organic alkali metal compound having sodium basicity (sodium ethoxide) as a carbodiimidization catalyst are placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, and stirred at 175 ° C. in a nitrogen stream. The reaction was continued until the NCO% measurement was 3.74%. The synthesis time was 21 hours. As a result of obtaining and analyzing the obtained isocyanate-terminated polytetramethylxylylene carbodiimide (average polymerization degree = 10), an absorption peak due to a carbodiimide group having a wavelength of around 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, as well as other absorption peak based on by-products Could not be confirmed. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 1886.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.

Example 4
100 g of tetramethylxylylene diisocyanate and 0.5 g of Lewis alkali basic organic alkali metal (lithium diisopropylamide) as a carbodiimidization catalyst are placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer and stirred at 175 ° C. under a nitrogen stream. The reaction was continued until the NCO% measurement was 3.74%. The synthesis time was 10 hours. As a result of analyzing the obtained isocyanate-terminated polytetramethylxylylene carbodiimide (average polymerization degree = 10), an absorption peak due to a carbodiimide group having a wavelength of about 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 1899.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.

Example 5
100 g of tetramethylxylylene diisocyanate and 0.5 g of an organic alkali metal (cesium acetate) having Lewis basicity as a carbodiimidization catalyst are placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, and stirred at 175 ° C. under a nitrogen stream. The reaction was continued until the NCO% measurement was 3.74%. The synthesis time was 21 hours. As a result of analyzing the obtained isocyanate-terminated polytetramethylxylylene carbodiimide (average polymerization degree = 10), an absorption peak due to a carbodiimide group having a wavelength of about 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 1904.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.

Example 6
100 g of tetramethylxylylene diisocyanate, 0.5 g of a Lewis basic organic alkali metal compound (potassium acetate) as a carbodiimidization catalyst, and 1.0 g of a phase transfer catalyst (18-crown 6-ether) were added to a reflux tube and a stirrer. The mixture was placed in a 300 ml reaction vessel with stirring and stirred at 175 ° C. under a nitrogen stream, and the reaction was carried out until the NCO% measurement was 3.74%. The synthesis time was 33 hours. As a result of analyzing the obtained isocyanate-terminated polytetramethylxylylene carbodiimide (average polymerization degree = 10), an absorption peak due to a carbodiimide group having a wavelength of about 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the polystyrene equivalent number average molecular weight was 1955.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.

Example 7
100 g of tetramethylxylylene diisocyanate, 0.5 g of an organic alkali metal compound (potassium tert-butoxide) having Lewis basicity as a carbodiimidization catalyst, and 1.0 g of a phase transfer catalyst (tetrabutylammonium 2-ethylhexanoate) The mixture was placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, stirred at 175 ° C. under a nitrogen stream, and the reaction was carried out until the result of NCO% measurement was 3.74%. The synthesis time was 20 hours. As a result of analyzing the obtained isocyanate-terminated polytetramethylxylylene carbodiimide (average polymerization degree = 10), an absorption peak due to a carbodiimide group having a wavelength of about 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 1910.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.

Example 8
100 g of tetramethylxylylene diisocyanate, 0.5 g of an organic alkali metal compound having Lewis basicity (potassium tert-butoxide) as a carbodiimidization catalyst and 1.0 g of a phase transfer catalyst (18-crown 6-ether) were added to a reflux tube and It put into the 300 ml reaction container with a stirrer, it stirred at 175 degreeC under nitrogen stream, and it reacted until it became 3.74% as a result of NCO% measurement. The synthesis time was 2 hours. As a result of analyzing the obtained isocyanate-terminated polytetramethylxylylene carbodiimide (average polymerization degree = 10), an absorption peak due to a carbodiimide group having a wavelength of about 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 1889.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.

Example 9
100 g of tetramethylxylylene diisocyanate, 0.5 g of an organic alkali metal compound having Lewis basicity (sodium ethoxide) as a carbodiimidization catalyst, and 1.0 g of a phase transfer catalyst (15-crown 5-ether) were added to a reflux tube and a stirring tube. The mixture was placed in a 300 ml reaction vessel equipped with a machine, stirred at 175 ° C. under a nitrogen stream, and reacted until the NCO% measurement was 3.74%. The synthesis time was 2 hours. As a result of analyzing the obtained isocyanate-terminated polytetramethylxylylene carbodiimide (average polymerization degree = 10), an absorption peak due to a carbodiimide group having a wavelength of about 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 1897.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.

Example 10
100 g of tetramethylxylylene diisocyanate, 0.5 g of an organic alkali metal compound (potassium tert-butoxide) having Lewis basicity as a carbodiimidization catalyst, and a phase transfer catalyst (end-capped polyethylene glycol: polyoxyethylene dimethyl ether number average molecular weight 550) 1 0.0 g was placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, and stirred at 175 ° C. under a nitrogen stream, and the reaction was carried out until the NCO% measurement was 3.74%. The synthesis time was 11 hours. An isocyanate-terminated polytetramethylxylylene carbodiimide (average polymerization degree = 10) was obtained. An absorption peak due to a carbodiimide group having a wavelength of around 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 1922.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.

Example 11
100 g of tetramethylxylylene diisocyanate, 0.5 g of an organic alkali metal compound (cesium acetate) having Lewis basicity as a carbodiimidization catalyst, and 1.0 g of a phase transfer catalyst (end-capped polyethylene glycol: polyoxyethylene dimethyl ether number average molecular weight 550) Were placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, and stirred at 175 ° C. under a nitrogen stream, and the reaction was carried out until the point of time when the NCO% measurement was 3.74%. The synthesis time was 10 hours. An isocyanate-terminated polytetramethylxylylene carbodiimide (average polymerization degree = 10) was obtained. An absorption peak due to a carbodiimide group having a wavelength of around 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the polystyrene equivalent number average molecular weight was 1931.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.

Example 12
100 g of tetramethylxylylene diisocyanate and 1.0 g of polyoxyethylene monomethyl ether having a number-average molecular weight of 550 having a phase transfer catalyst-like function are placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, and 1 at 175 ° C. under a nitrogen stream. After stirring for a period of time and reacting a hydroxyl group which is a terminal group of polyoxyethylene monomethyl ether with tetramethylxylylene diisocyanate by a urethanation reaction, an organic alkali metal compound having a Lewis basicity (potassium tert-butoxide) 0 as a carbodiimidization catalyst 0.5 g was added, and the reaction was continued until the NCO% measurement was 3.66%. The synthesis time was 11 hours.
The resulting isocyanate-terminated polytetramethylxylylene carbodiimide (average polymerization degree = 10) was obtained (however, a part of the carbodiimide terminal was sealed with polyoxyethylene monomethyl ether). An absorption peak due to a carbodiimide group having a wavelength of around 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 1924.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.

Example 13
100 g of tetramethylxylylene diisocyanate and 41 g of polyoxyethylene monomethyl ether (average molecular weight 550) having a phase transfer catalyst-like function are placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, and stirred at 175 ° C. for 1 hour in a nitrogen stream. Then, a hydroxyl group which is a terminal group of polyoxyethylene monomethyl ether was reacted with tetramethylxylylene diisocyanate by a urethanization reaction. (The molar ratio of tetramethylxylylene diisocyanate and polyoxyethylene monomethyl ether is 11: 2.) Subsequently, 0.5 g of an organic alkali metal compound (potassium tert-butoxide) having Lewis basicity was added as a carbodiimidization catalyst and stirred. The reaction was continued until the absorption of the isocyanate group having a wavelength of 2200 to 2300 cm ⁻¹ disappeared by infrared absorption (IR) spectrum measurement. The synthesis time was 8 hours. As a result of analyzing the obtained polyoxyethylene monomethyl ether-terminated polycarbodiimide (average polymerization degree 10), an absorption peak due to a carbodiimide group at a wavelength of about 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 2320.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.

Example 14
100 g of tetramethylxylylene diisocyanate and 41 g of polyoxyethylene monomethyl ether (average molecular weight 550) having a phase transfer catalyst-like function are placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, and stirred at 175 ° C. for 1 hour in a nitrogen stream. Then, a hydroxyl group which is a terminal group of polyoxyethylene monomethyl ether was reacted with tetramethylxylylene diisocyanate by a urethanization reaction. (The molar ratio of tetramethylxylylene diisocyanate to polyoxyethylene monomethyl ether is 11: 2.) Subsequently, 0.5 g of an organic alkali metal compound (potassium tert-butoxide) having Lewis basicity as a carbodiimidization catalyst and a phase transfer catalyst. (Tetrabutylammonium 2-ethylhexanoate) (1.0 g) was added and stirred, and the reaction was continued until the absorption of the isocyanate group having a wavelength of 2200 to 2300 cm ⁻¹ disappeared by infrared absorption (IR) spectrum measurement. The synthesis time was 4.5 hours. As a result of analyzing the obtained polyoxyethylene monomethyl ether-terminated polycarbodiimide (average polymerization degree 10), an absorption peak due to a carbodiimide group at a wavelength of about 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 2350.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.

Example 15
100 g of tetramethylxylylene diisocyanate and 41 g of polyoxyethylene monomethyl ether (average molecular weight 550) having a phase transfer catalyst-like function are placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, and stirred at 175 ° C. for 1 hour in a nitrogen stream. Then, a hydroxyl group which is a terminal group of polyoxyethylene monomethyl ether was reacted with tetramethylxylylene diisocyanate by a urethanization reaction. (The molar ratio of tetramethylxylylene diisocyanate to polyoxyethylene monomethyl ether is 11: 2.) Subsequently, 0.5 g of an organic alkali metal compound (potassium tert-butoxide) having Lewis basicity as a carbodiimidization catalyst and a phase transfer catalyst. (18-crown 6-ether) (1.0 g) was added and stirred, and the reaction was continued until the absorption of the isocyanate group having a wavelength of 2200 to 2300 cm ⁻¹ disappeared by infrared absorption (IR) spectrum measurement. The synthesis time was 4.5 hours. As a result of analyzing the obtained polyoxyethylene monomethyl ether-terminated polycarbodiimide (average polymerization degree 10), an absorption peak due to a carbodiimide group at a wavelength of about 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the polystyrene-equivalent number average molecular weight was 2385.
It was carried out to confirm the carbodiimidization catalyst (alkali metal) existence, since the absorption wavelength due to the isocyanurate of diphenylmethane diisocyanate, the absorption peak wavelength of about 1710 cm ^-1 longitudinal and wavelength 1411cm ^-1 was observed, the catalyst remains It was confirmed.

Example 16
100 g of tetramethylxylylene diisocyanate and 41 g of polyoxyethylene monomethyl ether (average molecular weight 550) having a phase transfer catalyst-like function are placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, and stirred at 175 ° C. for 1 hour in a nitrogen stream. Then, a hydroxyl group which is a terminal group of polyoxyethylene monomethyl ether was reacted with tetramethylxylylene diisocyanate by a urethanization reaction. (The molar ratio of tetramethylxylylene diisocyanate to polyoxyethylene monomethyl ether is 11: 2.) Subsequently, 0.5 g of an organic alkali metal compound (potassium tert-butoxide) having Lewis basicity as a carbodiimidization catalyst and a phase transfer catalyst. (Tetrabutylammonium 2-ethylhexanoate) (1.0 g) was added and stirred, and the reaction was continued until the absorption of the isocyanate group having a wavelength of 2200 to 2300 cm ⁻¹ disappeared by infrared absorption (IR) spectrum measurement. The synthesis time was 4.5 hours. Thereafter, 2.5 g of “Kyoward 600S” (manufactured by Kyowa Chemical Co., Ltd .: 2MgO · 6SiO ₂ · mH ₂ O) as a synthetic magnesium silicate-based adsorbent was placed in a reaction vessel and stirred at 150 ° C. for 2 hours under a nitrogen stream. Subsequently, suction filtration was performed using a glass suction filter to obtain polyoxyethylene monomethyl ether-terminated polycarbodiimide (average polymerization degree 10) after catalyst adsorption. As a result of analyzing the obtained polyoxyethylene monomethyl ether-terminated polycarbodiimide (average polymerization degree 10), an absorption peak due to a carbodiimide group at a wavelength of about 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 2360.
When the presence or absence of a carbodiimidization catalyst (alkali metal) was confirmed, it was confirmed that there was no change in the absorption peak immediately after mixing and after mixing and heating, and it was confirmed that the catalyst was sufficiently removed.

Reference example 1
100 g of tetramethylxylylene diisocyanate and 0.5 g of 3-methyl-1-phenyl-2-phospholene-1-oxide, which is a phosphorus compound as a carbodiimidization catalyst, are placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer. It stirred at 175 degreeC under airflow, and it reacted until it became 3.74% as a result of NCO% measurement. The synthesis time was 26 hours. As a result of analyzing the obtained isocyanate-terminated polytetramethylxylylene carbodiimide (average polymerization degree = 10), an absorption peak due to a carbodiimide group having a wavelength of about 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 1896.
When the presence or absence of a carbodiimidization catalyst (alkali metal) was confirmed, decarboxylation due to carbodiimidation of diphenylmethane diisocyanate was observed during heating, and an absorption wavelength of about 2138 cm ⁻¹ and a wavelength of 2112 cm ⁻ were observed by infrared absorption (IR) spectrum measurement. ^Since absorption peaks around ¹ were observed, it was confirmed that the catalyst remained.

Reference example 2
100 g of tetramethylxylylene diisocyanate and 0.5 g of 3-methyl-1-phenyl-2-phospholene-1-oxide, which is a phosphorus compound as a carbodiimidization catalyst, are placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer. The mixture was stirred at 195 ° C. under an air stream, and the reaction was carried out until the NCO% measurement was 3.74%. The synthesis time was 12 hours. As a result of analyzing the obtained isocyanate-terminated polytetramethylxylylene carbodiimide (average polymerization degree = 10), an absorption peak due to a carbodiimide group having a wavelength of about 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the polystyrene-equivalent number average molecular weight was 1020. Therefore, it was confirmed that the isocyanate itself decomposed at a high temperature and the carbodiimidization reaction did not proceed smoothly.
When the presence or absence of a carbodiimidization catalyst (alkali metal) was confirmed, decarboxylation due to carbodiimidation of diphenylmethane diisocyanate was observed during heating, and an absorption wavelength of about 2138 cm ⁻¹ and a wavelength of 2112 cm ⁻ were observed by infrared absorption (IR) spectrum measurement. ^Since absorption peaks around ¹ were observed, it was confirmed that the catalyst remained.

Comparative Example 1
100 g of hexamethylene diisocyanate (primary isocyanate) and 0.5 g of Lewis alkali basic organic alkali metal compound (potassium tert-butoxide) as a carbodiimidization catalyst were placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, and 175 under nitrogen flow. The mixture was stirred at 0 ° C., but the content was gelled after 3 hours. When the reaction product obtained was analyzed by infrared absorption (IR) spectrum measurement, the wavelength 2125Cm ^-1 absorption peak wavelength 1710 cm ^-1 before and after by the front and rear of the carbodiimide group, the absorption peak due to isocyanurate groups having a wavelength of about 1411cm ^-1 confirmed. Regarding the GPC measurement, since the obtained substance was gelled, it could not be measured.
Regarding the confirmation of the presence or absence of a carbodiimidization catalyst (alkali metal), the obtained substance was gelled, so measurement was impossible.

Comparative Example 2
100 g of 4,4′-dicyclohexylmethane diisocyanate (secondary isocyanate) and 0.5 g of an organic alkali metal compound having a Lewis basicity (potassium tert-butoxide) as a carbodiimidization catalyst were placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer. The mixture was stirred at 175 ° C. under a nitrogen stream, but the content was gelled after 3 hours. When the reaction product obtained was analyzed by infrared absorption (IR) spectrum measurement, wavelength 2120 cm ^-1 absorption peak wavelength 1710 cm ^-1 before and after by the front and rear of the carbodiimide group, the absorption peak due to isocyanurate groups having a wavelength of about 1411cm ^-1 confirmed. Regarding the GPC measurement, since the obtained substance was gelled, it could not be measured.
Regarding the confirmation of the presence or absence of a carbodiimidization catalyst (alkali metal), the obtained substance was gelled, so measurement was impossible.

Comparative Example 3
100 g of phenyl isocyanate and 0.5 g of an organic alkali metal compound (potassium tert-butoxide) having Lewis basicity as a carbodiimidization catalyst were placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, and stirred at 120 ° C. under a nitrogen stream. The reaction was continued until the absorption of the isocyanate group having a wavelength of 2200 to 2300 cm ⁻¹ disappeared by infrared absorption (IR) spectrum measurement. The synthesis time was 0.5 hours. When the reaction product obtained was analyzed by infrared absorption (IR) spectrum measurement, the absorption peak by wavelength 2121Cm ^-1 longitudinal and wavelength 2102Cm ^-1 before and after the carbodiimide group can not be confirmed, the wavelength 1710 cm ^-1 before and after the wavelength 1411Cm ^- Absorption peaks due to isocyanurate groups around ¹ were confirmed. The obtained substance was unnecessary in THF solvent, and molecular weight measurement by GPC was impossible.
Regarding the confirmation of the presence or absence of a carbodiimidization catalyst (alkali metal), the obtained substance was insoluble in diphenylmethane diisocyanate, so measurement was impossible.

Reference example 3
100 g of tetramethylxylylene diisocyanate and 41 g of polyoxyethylene monomethyl ether (average molecular weight 550) are placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, and stirred at 175 ° C. for 1 hour under a nitrogen stream to end the polyoxyethylene monomethyl ether. A hydroxyl group as a group and tetramethylxylylene diisocyanate were reacted by a urethanization reaction. (The molar ratio of tetramethylxylylene diisocyanate to polyoxyethylene monomethyl ether is 11: 2.) Subsequently, 3-methyl-1-phenyl-2-phospholene-1-oxide, which is a phosphorous compound as a carbodiimidization catalyst, was obtained in a 0. 5 g was added and stirred, and the reaction was continued until the absorption of the isocyanate group having a wavelength of 2200 to 2300 cm ⁻¹ disappeared by infrared absorption (IR) spectrum measurement. The synthesis time was 52 hours. As a result of analyzing the obtained polyoxyethylene monomethyl ether-terminated polycarbodiimide (average polymerization degree 10), an absorption peak due to a carbodiimide group at a wavelength of about 2118 cm ⁻¹ was confirmed by infrared absorption (IR) spectrum measurement. Absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after the absorption peak wavelength of about 1411cm ^-1, absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 absorption peak around, other absorption peak based on by-products I could not confirm. Furthermore, when GPC was measured, the number average molecular weight in terms of polystyrene was 2377.
When the presence or absence of a carbodiimidization catalyst (alkali metal) was confirmed, decarboxylation due to carbodiimidation of diphenylmethane diisocyanate was observed during heating, and an absorption wavelength of about 2138 cm ⁻¹ and a wavelength of 2112 cm ⁻ were observed by infrared absorption (IR) spectrum measurement. ^Since absorption peaks around ¹ were observed, it was confirmed that the catalyst remained.

Comparative Example 4
100 g of tetramethylxylylene diisocyanate and 0.5 g of an alkaline earth metal compound (magnesium ethoxide) having Lewis basicity as a carbodiimidization catalyst are placed in a 300 ml reaction vessel equipped with a reflux tube and a stirrer, and at 175 ° C. under a nitrogen stream. The mixture was stirred for 26 hours and the NCO% was measured and found to be 34.20%.
As a result of analyzing the obtained contents, an absorption peak due to a carbodiimide group having a wavelength of around 2118 cm ⁻¹ could not be confirmed by infrared absorption (IR) spectrum measurement. Further, the absorption wavelength due to isocyanurate, wavelength 1710 cm ^-1 before and after, based on the wavelength 1411Cm ^-1 absorption peak around the absorption wavelength due uretdione, wavelength 1765Cm ^-1 longitudinal, wavelength 1410 cm ^-1 before and after the absorption peak, other by-products absorb A peak could not be confirmed.

Gas chromatograph mass spectrometry (GC-MS)
The carbodiimide compounds obtained in Examples, Comparative Examples and Reference Examples were quantitatively analyzed by gas chromatography mass spectrometry (GC-MS) under the following conditions. The results are shown in Table 2.
[GC-MS measurement conditions]
Column: HP-5 (manufactured by Agilent, inner diameter 0.32 mm, film thickness 0.25 μm, length 30 m)
Carrier gas: helium, 1.0 mL / min
Injection conditions: 250 ° C., split ratio 1/50
Detection condition: FID method, 220 ° C
Column temperature condition: held at 40 ° C. for 5 minutes, then raised to 350 ° C. at 10 ° C./min. Ionization mode: EI
Ion source temperature: 230 ° C
Interface temperature: 350 ° C

The symbols in Table 1 are as follows.
TMXDI: Tetramethylxylylene diisocyanate TMI: 3-Isopropenyl-α, α-dimethylbenzyl isocyanate HDI: Hexamethylene diisocyanate HMDI: 4,4'-dicyclohexylmethane diisocyanate Ph-Iso: Phenyl isocyanate PTB: Potassium tert-butoxide EtONa: Sodium ethoxide LDA: lithium diisopropylamide sAc: cesium acetate EtOMg: magnesium ethoxide KAc: potassium acetate MPO: 3-methyl-1-phenyl-2-phospholene-1-oxide 18-crown: 18-crown 6-ether 15- Crown: 15-Crown 5-ether 18X: Tetrabutylammonium 2-ethylhexanoate PEG end capping: Polyoxyethylene Emissions dimethyl ether (number average molecular weight 550)
MP550: polyoxyethylene monomethyl ether having a number average molecular weight of 550 600S: 2MgO · 6SiO ₂ · mH ₂ O

A carbodiimide compound can be obtained according to Examples 1 to 16. By using the phase transfer catalyst (C) or the sealing agent (D-1) in Examples 6 to 16, the time required for carbodiimidization is shortened. became.
Moreover, a dimer and a trimer were not detected from the obtained carbodiimide compound.
On the other hand, according to Comparative Examples 1 and 2, since another isocyanate compound was blended instead of the aliphatic tertiary isocyanate compound (A), gelation occurred.
According to Comparative Example 3, since another isocyanate compound was blended instead of the aliphatic tertiary isocyanate compound (A), a carbodiimide compound could not be obtained.
According to the comparative example 4, since it replaced with the organic alkali metal compound (B) and magnesium ethoxide was mix | blended, the carbodiimide compound was not able to be obtained.
Further, as in Example 16, the catalyst could be removed by a simple operation.

Examples 17-26
Polyester polyurethane resin (Elastollan XNY585N-10 (manufactured by BASF)) dissolved in a mixed solution of DMF / THF is mixed with the carbodiimide compound shown in Table 3 shown in Table 3 in terms of solid content (active ingredient). It added so that it might become ratio, The polyester-type polyurethane resin composition (solution) was obtained.
This solution was applied onto a PET film which had been subjected to a release treatment using a control coater IMC-7013 and dried at 80 ° C. for 5 hours to obtain a 100 μm resin sheet. A strip sheet having a width of 10 mm and a length of 70 mm was produced from this resin sheet.
The tensile strength of the strip sheet was measured with a tensile tester (“3365”, manufactured by Instron).
In addition, the strip sheet is set in a highly accelerated life test apparatus (“PH-2KT-E”, manufactured by ESPEC CORP., Constant temperature and humidity chamber; temperature 80 ° C., relative humidity 95%) and subjected to wet heat treatment for 15 days. It was. The tensile strength of the strip sheet after the wet heat treatment was measured with a tensile tester.
The average value of the tensile strength of each of the five strip sheets before and after the wet heat treatment was calculated, and the average value of the tensile strength after the treatment with respect to the average value of the tensile strength before the treatment was calculated as the strength retention.
The results are shown in Table 3.

Comparative Example 5
A strip sheet was prepared in the same manner as in Example 17 except that a carbodiimide compound was not added to a polyester-based polyurethane resin (Elastollan XNY585N-10 (manufactured by BASF)) dissolved in a mixed solution of DMF / THF. Prepared and subjected to the same test as in Example 17.
The results are shown in Table 3.

As is clear from Table 3, the resin sheet obtained using the polyester polyurethane resin composition containing the carbodiimide compound was excellent in hydrolysis resistance.

Claims

A method for producing a carbodiimide compound, comprising a carbodiimide production step in which an aliphatic tertiary isocyanate compound (A) is reacted in the presence of a Lewis basic organic alkali metal compound (B).
The method for producing a carbodiimide compound according to claim 1, wherein the organic alkali metal compound (B) having Lewis basicity is at least one of a metal alkoxide, a metal amide, and a metal carboxylate.
The carbodiimide according to claim 1 or 2, wherein the aliphatic tertiary isocyanate compound (A) has at least one aromatic ring bonded to a tertiary carbon atom to which an isocyanate group is bonded. Compound production method.
The aliphatic tertiary isocyanate compound (A) is at least one of tetramethylxylylene diisocyanate and 3-isopropenyl-α, α-dimethylbenzyl isocyanate. A method for producing a carbodiimide compound.
In the carbodiimide production step, the aliphatic tertiary isocyanate compound (A) is reacted in the presence of the Lewis basic organic alkali metal compound (B) and the phase transfer catalyst (C). 5. The method for producing a carbodiimide compound according to any one of 4 above.
The method for producing a carbodiimide compound according to claim 5, wherein the phase transfer catalyst (C) is at least one of a crown ether, a quaternary ammonium salt, and a compound represented by the following general formula (1).

(In Formula (1), X and Y are each independently a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group. R 1 is an alkylene group having 2 to 3 carbon atoms. m is an integer of 2 to 500.)
Before the carbodiimide production step, during the production step, and at least one of the three time points after the production step, a part of the isocyanate group in the aliphatic tertiary isocyanate compound (A) is end-capped. A sealing step of sealing with an agent, wherein the end-capping agent is a compound (D-1) represented by the following general formula (2-1): The manufacturing method of the carbodiimide compound as described in 1 ..

(In the formula (2-1), Z is a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group. R 2 is an alkylene group having 2 to 3 carbon atoms. It is an integer of 500.)
Prior to the carbodiimide production step, during the production step, and at least one of the three time points after the production step, a part of the isocyanate group in the aliphatic tertiary isocyanate compound (A) is chain-extending agent. The chain extender is allowed to react with the compound, and the chain extender is a compound (D-2) represented by the following general formula (2-2): A method for producing a carbodiimide compound.

(In the formula (2-2), R 3 is an alkylene group having 2 to 3 carbon atoms. P is an integer of 2 to 500.)
The adsorbing and removing step of adsorbing and removing the organic alkali metal compound (B) having Lewis basicity using an adsorbent (E) after the carbodiimide producing step. The manufacturing method of the carbodiimide compound as described in 1 ..
The adsorbent (E) is a synthetic aluminum silicate adsorbent, synthetic magnesium silicate, acidic cation exchange resin, basic anion exchange resin, alumina, silica gel adsorbent, zeolite adsorbent, hydrotalcite The method for producing a carbodiimide compound according to claim 9, which is at least one of magnesium oxide-aluminum oxide solid solution, aluminum hydroxide, magnesium oxide, and aluminum hydroxide-sodium hydrogen carbonate coprecipitate (dorsonite).
The method according to any one of claims 1 to 10, for producing a stabilizer having a purity of 90% by mass or more and containing no phospholene oxides or having a phospholene oxide content of 1 mass ppm or less. A manufacturing method comprising the manufacturing method according to claim 1.
A process for producing a polyurethane, wherein a polyurethane, preferably a thermoplastic polyurethane, is obtained by reacting a polyol and a diisocyanate in the presence of a stabilizer.
The said stabilizer contains the aliphatic tertiary carbodiimide derived from an aliphatic tertiary isocyanate compound, and the manufacturing method of a polyurethane whose content of an alkali metal is less than 2000 mass ppm.
The blending amount of the aliphatic tertiary carbodiimide derived from the aliphatic tertiary isocyanate compound with respect to 100 parts by mass of the total amount of the polyol and the diisocyanate is 0.1 to 2 parts by mass, preferably 0.5 to 1 part by mass. The manufacturing method of the polyurethane of Claim 12 which is a part.
The aliphatic tertiary carbodiimide derived from the aliphatic tertiary isocyanate compound is metered in continuously or batchwise in liquid form, preferably at a temperature of 20-50 ° C., particularly preferably 25-35 ° C. The method for producing a polyurethane according to claim 12 or 13, wherein:
A process for producing a polyurethane, wherein a polyurethane, preferably a thermoplastic polyurethane, is obtained by reacting a polyol and a diisocyanate in the presence of a stabilizer.
A method for producing a polyurethane, wherein the stabilizer is a carbodiimide compound produced by the method for producing a carbodiimide compound according to any one of claims 1 to 10.
Use of the carbodiimide compound according to any one of claims 1 to 10 for preventing hydrolysis.
It contains a carbodiimide compound having an aliphatic tertiary isocyanate compound (A) as a structural unit and an alkali metal, and does not contain phospholene oxides, or the content of phospholene oxides is 1 mass ppm or less. A carbodiimide composition.
The carbodiimide composition according to claim 17, further comprising a phase transfer catalyst (C).
It contains a carbodiimide compound having an aliphatic tertiary isocyanate compound (A) as a structural unit and an alkali metal, and does not contain phospholene oxides or the content of phospholene oxides is 1 mass ppm or less. There is a stabilizer.
The stabilizer according to claim 19, further comprising a phase transfer catalyst (C).
An ester resin composition comprising the carbodiimide composition according to claim 17 or 18 and an ester resin.
The ester resin composition according to claim 21, wherein a content of the carbodiimide composition is 0.2 to 5.0 parts by mass with respect to 100 parts by mass of the ester resin.
An ester resin composition comprising the stabilizer according to claim 19 or 20 and an ester resin.